Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/46—Removing components of defined structure
  • B01D53/54—Nitrogen compounds
  • B01D53/56—Nitrogen oxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
  • C01B21/38—Nitric acid
  • C01B21/40—Preparation by absorption of oxides of nitrogen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
  • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Definitions

• the present invention relates to an improved process for treating a gaseous stream containing nitrogen oxides and oxygen and, more especially, to the separation of nitrogen oxides from the gaseous effluent from a nitric acid synthesis facility, and to the use of such process for the purification of certain residual gases.
• nitric acid via oxidation of ammonia with oxygen has long been known to this art.
• the initial reaction which is conducted at elevated temperature produces nitric oxide, NO, which oxide is then itself oxidized by oxygen at a lower temperature, to produce nitrogen peroxide, NO 2 , which in turn undergoes with water, in oxido-absorption columns, or towers, a dismutation reaction producing nitric acid and nitric oxide.
• the nitric oxide is in its turn re-oxidized by the remaining oxygen and the process continues with dismutation.
• a conventional plant for the production of nitric acid typically comprises two, or preferably three plate absorption towers.
• the oxygen partial pressure and the partial pressures of the nitrogen oxides (NO and NO 2 ) in the gas feed are such that the oxidation and absorption process slows down to such a point that it would be necessary to considerably increase the number of plates in the column in order to remove the nitrogen oxides which have not been converted into nitric acid and which are present in the residual gas stream. It is for this reason that, in order to avoid excessively high capital investment, the residual gases are discharged to atmosphere containing substantial amounts of nitrogen oxides, for example, between 1000 and 2000 vpm (volumes per million).
• Discharging gas in this manner suffers from two serious disadvantages: on the one hand, the discharged gases constitute a loss in production, which can be assessed at about 1% or more, and, on the other hand, they cause a serious problem as regards environmental pollution.
• the different national laws which have been recently published require the residual or vent gases to contain substantially smaller amounts of nitrogen oxides (NO x ).
• NO x nitrogen oxides
• the French standard requires a level of less than 400 vpm while the U.S. standard requires a level less than 255 vpm.
• the height of the gas-liquid emulsion formed on each plate is relatively small, on the order of about 0.1 meter, in order to promote the oxidation of NO to NO 2 in the gaseous phase at a slow rate.
• the ratio R between the volume of column between two successive plates, and the volume occupied by the gas-liquid emulsion between said successive plates is advantageously higher than 7, and preferably is approximately 9.
• the ratio K between the liquid retention volume in m 3 in the corresponding section of the gas/liquid phase contactor, with the treated gas flow rate being in Nm 3 /h, is lower than 3.5 ⁇ 10 -4 hour, and preferably is approximately 2.5 ⁇ 10 -4 hour.
• a major object of the present invention is to provide for the enhanced efficiency of oxidation/absorption of the NO x in gaseous feedstreams comprising the same, in amounts of less than 6000 vpm and preferably less than 2500 vpm, said oxidation/absorption being conducted countercurrently in the presence of oxygen, in a gas/liquid phase contactor, with said liquid phase comprising an aqueous solution of dilute nitric acid.
• the present invention features the improved transfer of said NO x species into the liquid phase, with such improved transfer being effected by increasing the residence time of the liquid phase in the corresponding section of the phase contactor to a value such that the ratio K between (i) the liquid retention volume (in m 3 ) in said corresponding section of the phase contactor and (ii) the rate of flow of the gas stream (in Nm 3 /h), is greater than 5 ⁇ 10 -4 hour for 6000 vpm, and greater than 3.5 ⁇ 10 -4 for 2500 vpm.
• the immediately foregoing reflects that the height of the gas/liquid emulsion is increased on all, or on some of the plates in said corresponding section of the phase contactor, with all other parameters being equal as regards the gas and liquid rates of flow, the dimensions of the columns, the number, spacing and constitution of the individual plates, the operating pressure, and the composition of the gaseous stream to be treated and that of the aqueous solution.
• the topic invention provides a facile and yet economic means for enhancing the production of nitric acid, while at the same time providing for venting to the atmosphere of markedly less polluting residual off-gases.
• the gaseous feedstream to be treated originates from the air or oxygen combustion of ammonia and contains nitrogen, oxygen and the nitrogen oxides NO and NO 2 , said nitrogen oxides being present therein in an amount which does not exceed 6000 vpm.
• the amount of oxygen present in the gas is not critical, provided that it is in excess of that amount required for the oxidation of NO to NO 2 in gaseous phase, and for the oxidation of HNO 2 to HNO 3 in the liquid phase, i.e., HNO 2 +1/2O 2 ⁇ HNO 3 .
• an oxido-absorption column comprising an assemblage of plate-type columns which are modified in accordance with the present invention in such a way that, under stable operating conditions, the height of the liquid emulsion is increased therein, are determined by the aforenoted conditions, namely, that the gas which is treated therein has a NO x content of less than 6000 vpm.
• the subject alteration in the apparatus is located on the last downstream plates of the installation.
• the modification according to the invention occurs in all or some of the last thirty plates, preferably the last twenty plates.
• the values in respect of the ratio K as defined hereinbefore, in accordance with the invention, for a countercurrent oxido-absorption apparatus determine, in the specific case of a plate-type column, the values of the ratio R, also as hereinabove defined, such that R is less than 7, and preferably is less than 4.5.
• the lower limit on the value for R is theoretically not critical but, when reducing the value of R, the occurrence of the "weeping" phenomenon should be avoided, which occurs when all or a fraction of the liquid on the plate flows through the holes in the plate towards the plate below, instead of passing through the overflow means.
• the lower value of R is therefore governed by practical considerations appropriate to each type of column and plate, and the operating parameters thereof.
• the aqueous solution employed is water or preferably a dilute aqueous solution of nitric acid.
• the HNO 3 concentration thereof is advantageously less than 8 N and preferably is less than 5 N.
• the temperature used in the oxido-absorption columns is close to ambient temperature.
• the pressure used is not critical. An increase in the pressure makes it possible to increase the level of oxido-absorption efficiency. Operation is usually conducted at a pressure of between 1 and 20 bars absolute, preferably 1 or 12 bars absolute.
• the process according to the invention is simply carried out utilizing countercurrent gas/liquid phase contactors which are basically known to this art, such as, for example, columns equipped with perforated plates, which are provided with a tube for the overflow of liquid to the plate below, and a bowl into which the tube for the overflow of liquid from the plate above dips, the flow of the aqueous phase being vertically downwardly descending and the flow of the gaseous stream being upwardly vertically ascending or other apparatus providing good gas/liquid contact can conveniently be used.
• countercurrent gas/liquid phase contactors which are basically known to this art, such as, for example, columns equipped with perforated plates, which are provided with a tube for the overflow of liquid to the plate below, and a bowl into which the tube for the overflow of liquid from the plate above dips, the flow of the aqueous phase being vertically downwardly descending and the flow of the gaseous stream being upwardly vertically ascending or other apparatus providing good gas/liquid contact can conveniently be used.
• the overflow tube or conduit is extended upwardly to a height which is calculated for the desired height of the emulsion above the plates, in dependence upon the operating parameters of the column (liquid flow rate, pressure drop in the dry state, etc.).
• the invention is particularly suitable for reducing the NO x content of an off-gas emanating from a nitric acid plant, and entailing alteration of the last in the series of plates of the oxido-absorption tower, thereby producing a residual gas with a reduced NO x content and producing an increase in the level of efficiency of the nitric acid oxido-absorption unit.
• the gases were charged into the unit at a flow rate of 52,000 Nm 3 /hour, at a pressure of 4 bars absolute and a temperature of 18° C., the diameter of the column was 5 m and the percentage of oxygen in the feedstream approximately 3.5%.
• the distance between plates was 0.9 meter and the height of the gas-liquid emulsion was 0.1 m, thus defining a ratio R of 9.
• the absorption solution was water which was introduced to the top of the apparatus at a flow rate of 5.7 m 3 /hour.
• the same apparatus as described in the Comparative Example was used, under the same operating conditions.
• the heights of the gas-liquid emulsion on the 20 plates of the third column were adjusted respectively to values such that the ratio R was 4.5, 3 and 2.25, by modifying the height of the overflow assemblies.
• the NO x content (in vpm) in the gases discharged to atmosphere was measured.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Environmental & Geological Engineering (AREA)
• Health & Medical Sciences (AREA)
• Biomedical Technology (AREA)
• Inorganic Chemistry (AREA)
• Analytical Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Treating Waste Gases (AREA)
• Gas Separation By Absorption (AREA)
• Catalysts (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

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Publications (1)

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Cited By (6)

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Citations (5)

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• 1980
  • 1980-07-11 FR FR8015461A patent/FR2486513A1/fr active Granted
• 1981
  • 1981-06-30 EP EP81401045A patent/EP0047191B1/fr not_active Expired
  • 1981-06-30 US US06/279,000 patent/US4372935A/en not_active Expired - Lifetime
  • 1981-06-30 DE DE8181401045T patent/DE3163069D1/de not_active Expired
  • 1981-06-30 AT AT81401045T patent/ATE7013T1/de not_active IP Right Cessation
  • 1981-07-09 MX MX819530U patent/MX7389E/es unknown
  • 1981-07-09 GR GR65457A patent/GR75648B/el unknown
  • 1981-07-10 ES ES503831A patent/ES8301452A1/es not_active Expired
  • 1981-07-10 NO NO812362A patent/NO156896C/no unknown
  • 1981-07-10 BR BR8104430A patent/BR8104430A/pt not_active IP Right Cessation
  • 1981-07-10 ZA ZA814706A patent/ZA814706B/xx unknown
  • 1981-07-10 TR TR21336A patent/TR21336A/xx unknown
  • 1981-07-10 CA CA000381537A patent/CA1166427A/fr not_active Expired
  • 1981-07-10 JP JP56107202A patent/JPS5751107A/ja active Granted

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